Process for making higher aliphatic alcohols



Patented May 13, 1941 moon ss FOR. MAKING HIGHER ALIPHATIO ALconoLs WilhelmNormann, Chemnitz, Germany, assignor, by mesne assignments, to American Hyalsol Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application January 21, 1931, Ser r i UNITED STATES PATENT I OFFICE.

No. 510,326. In Germany January 27, 1930 18 Claims.

'by catalytic reduction by means of hydrogen upon working in accordance with certain conditions. Finely divided metallic copper which may be deposited on a suitable carrier, for example, kieselguhr, is used as the catalyst. If hydrogen be caused to act on the fatty acid ester to, be reduced, at 300-400 C., in the presence of the copper catalyst and under a pressure of 100-200 atmospheres, the corresponding alcohol will be obtained in a very good yield. The unexpected fact has now been discovered that other known catalytic metals, for example nickel, platinum and palladium, at the temperature and pressure conditions stated, produce a further reduction to the hydrocarbon stage, so that only very little alcohol is obtained. Thus, metallic copper shows the specific efiect that it catalyzes only the first step of the reduction process, namely the conversion of the ester into the alcohol, but not the further reduction into the hydrocarbon, so that it becomes possible to obtain the product of the first reduction step nearly quantitatively.

Erample 0111125011 (lauric alcohol) is obtained with a smoothly proceeding reaction resulting in a very good yield.

It is also possible to use, instead of the ethyl ester of lauric acid, the ester mixture which results uponesterifying all the fatty acids of cocoanut fat with ethyl alcohol or some other lower aliphatic alcohol. When the mixture of ethyl esters isemployed, the fraction boiling between 255 and 275 C. is used. The esters of other higher fatty acids with univalent alcohols, as well as the corresponding glycerin esters may also be processed in an analogous way. Thus the conversion of the naturally occurring fatty acid glycerids into other esters may be eliminated and the mixtures of glycerids or individual glycerids isolated therefrom may be subjected to the reduction in the manner described.

The products obtained may be used for many commercial purposes, for example in the various branches of the art of textile improvement, and y may be employed without further refining or separation. They are in particular excellently suitable for making ,sulfurized products, because, even if they do not contain of alcohols, yet they do contain nearly 100% of sulfurizable constituents, which may include also the admixed unsaturated compounds.

Having thus described the invention, what is claimed as-new and desiredto be secured by Letters Patent is:

1. The process of preparing lauric alcohol coni- 4 prising treating the ethyl ester of lauric acid with hydrogen in the presence of metalliccopper at a pressure of about 100-200 atmospheres and at a temperature between 300 and 400 C.

2. In the process of converting ethyl laurate into the corresponding alcohol, the step which comprises reacting a mixture of said ester and hydrogen at a temperature in excess of 300 C.

and under a super-atmospheric pressure in the presence of a copper hydrogenating catalyst.

3. The process of preparing higher aliphatic alcohols having at least eight carbon atoms comprising treating an alkyl ester of an aliphatic acid having more than eight carbon atoms in the'acid radical with hydrogen in the presence of a metallic copper catalyst at a temperature in excess of 300 C. and under superatmospheric pressure.

4. The process in accordance with claim 3 wherein the ester of the higher aliphatic acid is a fatty acid ester.

5. The process for the production of alcohols of high molecular-weight comprising reacting an ethyl ester of an acid obtained from a natural fat or oil having at least 8 carbon atoms in the acid radical with hydrogen at a temperature of from 300 to 400 C. under a superatmospheric pressure in the presence of a copper catalyst.

6. In the process of converting ethyl laurate,

into the corresponding alcohol, the step which comprises reacting a mixture of said ester and hydrogen at a temperature below 400 0., at which reduction of the lauric acid radical of the ester to lauryl alcohol takes place, and under a super-atmospheric pressure in the presence of a copper containing hydrogenating catalyst.

7. The method of producing an octodecyl alcohol by catalytically hydrogenating a lower allmixing a carboxylic acid ester having at least 8 carbon atoms in the acid radical in the liquid phase with a copper-containing hydrogenation catalyst, introducing hydrogen into contact with said mixture and causing the same to act thereon at a temperature above 300 C. at a pressure above 100 atmospheres until the carboxylic acid radicals are reduced to alcohols.

--9. The process of producing alcohols corresponding in number of carbon atoms to the fatty acids of cocoanut oil which comprises heating an alkyl ester of an aliphatic acid derivable from cocoanut oil to a temperature of from 300 to 400 13. The process for the production of alcohols containing more than 8 carbon atoms which comprises reacting an ester of an aliphatic carboxylic acid containing more than 8 carbon atoms in the acid radical, in the liquid phase with hydrogen at a'temperature of from 300-400 C.

- radical of an alkyl laurate into lauryl alcohol,

under a superatmospheric pressure in the pres- L ence of hydrogen and an activated copper consuper-atmospheric pressure in the presence of a copper-containing hydrogenating catalyst.

11. The process of producing an alcohol from a lower molecular alkyl ester of a higher molecular aliphatic carboxylic acid, said alcohol corresponding in number of carbon atoms to said acid, which comprises treating said ester of an aliphatic carboxylic acid, the number of carbon atoms in said acid being greater than the number of carboxyl groups and more than 8 in the presence of hydrogen, at a temperature between about 300C. and 400 C. and under a superatmospheric pressure .in the presence of a hydrogenating catalyst composed of copper.

12. The process for the production of alcohols of high molecular weight from esters'of aliphatic carboxylic acids, saidalc'ohols corresponding in number of carbon atoms to said acids, which the step which comprises reducing the said acid radical with hydrogen at a temperature above about 300 C. and under a superatmospheric pressure in the presence of a hydrogenating copper catalyst.

15. The process of converting the lauric acid radical of ethyl laurate into lauryl alcohol which comprises reacting a mixture of said ester and hydrogen at a temperature of from 300-400 C. and under 'a pressure of from 100-200 atmospheres in the presence of a copper-containing hydrogenating catalyst.

16. A method of producing higher molecular alcohols by catalytically hydrogenating an ester of an aliphatic carboxylic acid containing more than 8 carbon atoms in the acid radical, which comprises heating said ester at a temperature below 400 C. under superatmospheric pressure in the presence of hydrogen and a copper-containing hydrogenation catalyst until the ester is substantially converted into alcohol containing more than 8 carbon atoms. v

17. A process which comprises subjecting esters of aliphatic carboxylic acids containing at least 8' carbon atoms in the acid radical to the action of hydrogen and a hydrogenating catalyst at a temperature below 400 C. and under superatmospheric pressure, whereby the higher molecular carboxylic radicals are reduced at least as far as the alcohol stage and reduction products are obtained which include alcohols and other reduction products corresponding in number of carbon atoms tothe carboxylic radicals treated.

18. A process which comprises heating, esters of aliphatic carboxylic acids having at least 8 carbon atoms in the acid radical at a temperature above 300 C. under superatmospheric pressure in the presence of hydrogen and a hydrogenation catalyst containing a member selected from the group consisting of copper, nickel, platinum and palladium, whereby reduction products are obcomprises reacting an esterof an aliphatic carpressure of from 100-200 atmospheres in the presence of a copper hydrogenating catalyst.

tained containing alcohol corresponding in number of carbon atoms to the carboxylic radicals of the esters together with other constituents, substantially all of which products are capable 01 being sulfurized to form textile treating agents.

WILHEIM NORMAN N. 

